P-nitro-o-methyl sulfonebenzene azo-n-beta-cyanoethyl-n-hydroxyalkylaniline dye compounds



Patented Jan. 3, 1950 UNITED STATES PATENT OFFICE P-NITRG-O-METHYL SULFONEBENZENE AZO-N-fl-CYANOETHYL- N -HYDROXY ALKYLANILINE DYE COM0UNDS Joseph B. Dickey, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application July 26, 1946, Serial No. 686,438

CHZCHZCN CH3 wherein R stands for a member selected from the group consisting of the p-hydroxyethyl group, the fl-hydroxypropyl group and the 'y-hydroxypropyl group are unusually valuable dyes for coloring textile materials comprising cellulose carboxylic ester fibers, in which ester the acid radical contains from 2 to 4 carbon atoms. They are especially useful for the coloration of cellulose acetate textile materials.

The new azo compounds of my invention dye the aforesaid textile materials red shades of exceptional fastness to light and gas. Their outstanding utility is apparent from the fact that they yield dyeings on cellulose acetate textile materials which are three to five times as fast to light as the dyeings obtained with the dyes:

CHzCHOHCHnOH and the dye 0 Hz 0 Hg 0 H which is one of the best, if. not the best, scarlet azo dyes now available for dyeing cellulose acetate textile materials.

Further I have found that the dye compounds of my invention yield dyeings on cellulose acetate textile materials which are of greatly superior light iastness (usually 3 to 5 times) to the dyeings obtained on cellulose acetate textile materials with the dyes having the general formula:

wherein X stands for a hydrogen atom, a chlorine atom, a bromine atom, a methyl group or a methoxy group, Z stands for a hydrogen atom, a methyl group, a methoxy group or an acetylamino group, R1 stands for a p-hydroxyethyl group, a p-hydroxypropyl group, a 'y-hydroxypropyl group or a p -dihydroxypropyl group and R2 stands for a B-cyanoethyl group, a methyl group, an ethyl group or a ,B-hydroxyethyl group.

In addition, the aqueous nitrous acid fastness properties of the dyeings obtained on cellulose acetate with the new dye compounds of the invention are considerably superior to that of the dyeings obtained with the scarlet azo dyes now available for dyeing cellulose acetate, as for example, p-nitrobenzeneazo-N-ethyl-N-fl-hydroxyethylaniline, previously referred to. The advantages of my new dye compounds could not have been predicted.

It is an object of my invention to provide new azo dye compounds. Another object is to provide a satisfactory process for the preparation of the new azo dye compounds of my invention. A further object is to provide cellulose carboxylic ester textile materials colored with the new azo compounds of the invention. A particular object is to provide dyed cellulose acetate textile materials of outstanding fastness to light and gas.

The new azo dye compounds of my invention can be prepared by diazotizing 1-amino-2-methylsulfonel-nitrobenzene and coupling the diazonium salt obtained with a compound having the formula CHzCHzON wherein R stands for the B-hydroxyethyl group, the ,B-hydroxypropyl group or the v-hydroxypropyl group.

The following examples illustrate the azo com- 3 pounds of my invention and their manner of preparation Example 1.-Preparation of 4-m't1'o-2-methylsulfonebenzeneazo 4-(N -ficyanoethg l -N-B- hydroaryethyl) -am'line 7.6 grams of sodium nitrite are dissolved in 50 cc. of sulfuric acid (sp. gr. 1.84) while keeping the temperature below 70 C. The resulting mixture is cooled to C.- C. and 109 cc. of glacial acetic acid are added with stirring while keeping the temperature below 20 C.- C. The reaction mixture is cooled to 15 C. and 21.6 grams of 1 amino-Z-methylsulfone 4 nitrobenzene are gradually added with stirring and then 100 cc. of glacial acetic acid are added. Throughout the diazotization reaction which takes place the mixture is stirred and the temperature kept at 10 C.- 15 C. Upon completion of the diazotization reaction sufiicient sulfamic acid or urea is added to destroy any nitrous acid present in the reaction mixture. The diazonium solution formed is poured onto 500 grams of cracked ice.

19 grams of N-B-cyanoethyl-N-fi-hydroxyethylaniline are dissolved in 200 cc. of water to which has been added 15 cc. of 36% aqueous hydrochloric acid. The reaction mixture resulting is cooled to 15 C.-20 C. The diazonium solution prepared as described above is added with stirring. Throughout the coupling reaction which takes place the temperature is maintained at 15 C.- 20 C. Coupling is completed by adding sodium bicarbonate until the reaction mixture is just neutral to Congo red paper. The dye compound formed is recovered by filtration, washed Well with water and dried. It has the formula:

CH OHgOH and colors cellulose acetate textile materials red This compound is prepared by .substituting 19.4 n

grams of N-fl-cyanoethyL- N-p-hydroxypropylaniline for N-[i-cyanoethyl N -fi-.hydroxyethylaniline in the reaction described in Example 1. The diazotization, coupling and .dye recovery operations are carried out in accordance with the procedure of Example 1. The dye compound obtained has the formula:

omononom It colors cellulose acetate textile materials red shades.

Example 3.--Preparation of 4-nitro-2-methylsulfonebenzeneazo 4' (N-p-cyanoethyl-N- -hydromypropyl) -.an.il,ine

h s dy c mp und is p par d y su stitut 19.4 grams of N-fi-cyanoethyl-N-' -hydroxypropylaniline for N-B-cyanoethyl-N-fi-hydroxyethyli e in the rea tion d scri ed in Exa ple 1- cellulose acetateebutyrate.

The diazotization, coupling and dye recovery operations are carried out in accordance with the procedure described in Example 1. The dye compound obtained has the formula:

Preparation of N-B-cyanoethyZ-N-p-hydro:cyethylam'line 123 grams of vN-fi-hydroxyethylaniline,53 grams .of acrylonitrile and 10 cc. of glacial acetic acid are placed in a round-bottom flask and heated on a steam bath under a reflux condenser for 150 hours. The reaction mixture is then distilled through an eflicient fractionating column (e. g. a Penn State column). 154 grams of N-o-cyanoethyl-II-5-hydroxyethylaniline boiling at 205- 207 C./8 mm. are obtained. By the substitution of an equivalent gram molecular weight of N-fihydroxypropylaniline and N-y-hydroxypropylaniline for the N-B-hydroxyethylaniline of the foregoing example, N-p-cyanoethyl-N-B-hydroxypropylaniline and N-B-cyanoethyLN- -hydroxypropylaniline, respectively, are obtained.

1 amino 2,- methylsulfone 4 nitrobenzene (known also as Z-amino-5-nitrophenylmethylsulfone) is a known compound and accordingly, a description of its preparation is deemed unnecessary.

Cellulose .carboxylic esters which are employed in the manufacture of textile materials include the partially hydrolysed as well as the unhydrolysed cellulose acetates, cellulose propionates and cellulose butyrates and the partially hydrolysed as well as the unhydrolysed mixed esters of cellulose, such as cellulose acetate-.propionate and All of these cellulose carboxylic esters consist of a cellulose portion or radical and an acid radical which contains from 2 to 4 carbonatoms.

The azo dye compounds of my invention can be applied to the textile materials indicated hereinbefore in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as Turkey red oil, sulfite cellulose solution, soap, or an oleyl glyceryl sulfate and the resulting paste is dispersed in water. lhe dye bath thus prepared is heated to a temperature approximating C.- C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to C.- C. and maintained at this point until dyeing is complete, usually one half hour to two hours. Upon completion of the dyeing operation the textile material is removed from the dyebath, washed with soap, rinsed well with water and dried.

As the azo dye compounds of the invention possess good affinity for the textile materials named herein and dye these materials readily they can be .used in jigdyeing operations in which somewhat lower temperatures (65 C.-'75 C., for

.75 example) than those just mentioned, are ordi- 6 narily employed. Widely varying amount of dye 3. The azo dye compound having the formula: can be used in the dyeing operation. The amount OHzCHaCHnOH of dye used can be, for example, to 3% (by N O weight) of that of the textile material although lesser or greater amounts of dye can be employed. 5 CH8 cmomoN I claim: 1. The azo dye compounds having the general formula: JOSEPH B. DICKEY.

R Nor O 10 REFERENCES CITED omomoN The following references are of record in the CHI file of this patent:

g th UNITED STATES PATENTS wherein R stands for a member selected from e group consisting of the fl-hydroxyethyl group and 53212 g ffi g 'i 'Q fi g gfi gga havm the formula. 2,109,024.- Holzach Feb. 22,1938 e y g 2,156,446 Bock May 2,1939 2,173,053 Hitch Sept. 12,1939 NOrQN=NGN 2,387,987 Felix Oct. 30,1945

OH s Hfl FOREIGN PATENTS I 8 Number Country Date 188,205 Switzerland Dec. 15,1936 640,404 Germany Jan. 4, 1937 216,157 Switzerland Aug. 15, 1941 

1. THE AZO DYE COMPOUNDS HAVING THE GENERAL FORMULA: 